Sunscreen composition

ABSTRACT

The present invention relates to a composition having UV protection properties, charaterized in that the formulation comprises at least one encapsulated organic sunscreen and does not penetrate the skin essentially.

The present invention relates to sunscreen compositions.

A suntan of the skin to whatever degree is regarded in today's societyas attractive and as an expression of vigour and sportiness. As well asthis desired effect of the sun on the skin, a number of undesiredsecondary effects arise, such as sunburn or premature skin ageing andthe development of wrinkles. In the meantime, a number of performance UVfilters have been developed which, applied to the skin in the form ofcreams, lotions or gels, can effectively delay the development ofsunburn even when the incidence of solar rays is relatively high. The UVfilter present in the pharmaceutical or cosmetic composition forms afilm or a layer on the surface of the skin and does not penetrate intodeeper skin layers with other care substances present in thecomposition. Known UV filters or sun protection agents thus act only byabsorbing certain regions of sunlight, meaning that this radiationcannot penetrate into deeper layers of the skin. As is known, the mosthazardous part of solar radiation is formed by the ultraviolet rayshaving a wavelength of less than 400 nm. The lower limit of theultraviolet rays which reach the surface of the earth is limited by theabsorption in the ozone layer to about 280 nm. The sun protectionfilters which are nowadays customary in cosmetics absorb in a wavelengthrange from 280 to 400 nm. This range includes UV-B rays having awavelength between 280 and 320 nm, which play a decisive role in theformation of a solar erythema, and also UV-A rays, having a wavelengthbetween 320 and 400 nm, which tan the skin but also age it, favour thetriggering of an erythematous reaction or can exacerbate this reactionin certain people or even trigger phototoxic or photoallergic andirritative reactions.

The object of care cosmetics is wherever possible to obtain theimpression of a youthful skin. In principle, there are various ways ofachieving this object. For example, existing skin damage, such asirregular pigmentation or the development of wrinkles can be smoothedout by covering powders or creams. Another approach is to protect theskin against environmental influences which lead to permanent damage andthus ageing of the skin. The idea is therefore to intervene in apreventative manner and thus to delay the ageing process. One example ofthis is the UV filters already mentioned which, as a result ofabsorption of certain wavelength regions, prevent or at least reduceskin damage. Depending on the position of their absorption maxima, UVabsorbers for cosmetic and dermatological compositions are divided intoUV-A and UV-B absorbers. UV-A absorbers are usually also absorbing inthe UV-B region and thus alternatively also being referred to asbroad-band absorbers or broad-band filters.

It is known that inorganic UV filters such as Titanium dioxide do notpenetrate the skin, while several sunscreen compositions comprisingsoluble organic UV filters are said to penetrate the skin. Furthermoreit is desired to induce a protective UV absorbing layer on top of theskin's surface in order to prevent any possible interactions of theapplied filters with the skin.

Therefore there was a need for formulations with high Sun ProtectionFactor which are less penetrating the skin.

A first embodiment of our invention therefore is a composition having UVprotection properties, characterised in that the formulation comprisesat least one encapsulated organic sunscreen and does not penetrate theskin essentially.

Preferably the at least one encapsulated organic sunscreen isencapsulated in capsules mainly consisting of organic polymericmaterials and/or inorganic oxidic materials.

Suitable capsules can have walls made of inorganic or organic polymers.For example, U.S. Pat. No. 6,242,099 B1 describes the preparation ofsuitable capsules with balls made of chitin, chitin derivatives orpolyhydroxylated polyamines. Capsules which are to be used particularlypreferably according to the invention have walls which can be obtainedby a sol-gel process, as is described in the applications WO 00/09652,WO 00/72806 and WO 00/71084. Preference is given here in turn tocapsules whose walls are made of silica gel (silica; undefined siliconoxide hydroxide). The preparation of corresponding capsules is known tothe person skilled in the art, for example, from the cited patentapplications, the contents of which also expressly belonging to thesubject-matter of the present application.

Here, the capsules are present in formulations according to theinvention preferably in amounts which ensure that the encapsulated UVfilters are present in the formulation in the typical amounts givenbelow.

The minimal particle size of those capsules depends on necessary size toprevent penetration of the skin. On the other side, the maximum particlesize is limited by the application needs. The capsules shouldn't bediscernible with blank eyes. Preferred capsules have a average particlesize in the range from about 10 nm up to about 10000 nm, preferably upto 5000 nm and most preferred up to 2000 nm.

The compositions according to our invention do not penetrate the skinessentially. This means the compositions do penetrate the skin in alower amount than conventional compositions comprising soluble organicUV filters which are not encapsulated. The penetration can for examplebe measured according to COLIPA (The European Cosmetic Toiletry andPerfumery Association); 1997; Guidelines; “Cosmetic ingredients:Guidelines for percutanous absorption/penetration” with a Franz typeDiffusion Cell or according to Weigmann et al. in Skin Pharmacol. Appl.Skin Physiol. 12 (1999) 34-45. Preferred compositions of our inventionshow a reduction of skin penetration measured with at least one of thismethods of at least 10% preferably at least 20% and even more preferredat least 50% compared to compositions with the same but unencapsulatedUV filters.

In principle, all known UV filters are suitable for compositionsaccording to our invention. The filters can preferably be includedeither in solid, dispersed or in encapsulated form. All organicUV-filters mentioned in the list below are preferred as encapsulatedfilters. Especially preferred are 2-Ethylhexl-Methoxy Cinnamaic-Acidand/or 2-ethylhexyl-2-cyano-3,3-diphenylacrylate combined withButylmethoxy Dibenzoylmethane and/or2-ethylhexyl-2-cyano-3,3-diphenylacrylate, Homomethyl Salicylate orOctyl Salicylate alone or in combination with other filters.

In one preferred embodiment of our invention the composition comprisesno organic sunscreen agents in soluble form. In another preferredembodiment the compositions contain an amount of water soluble organicUV filters, preferably selected from 2-phenylbenzimidazole-5-sulfonicacid, and its potassium, sodium and triethanolamine salts (e.g. Eusolex®232) or Disodium Phenyl Dibenzimidazole Tetrasulfonate (e.g.Neoheliopan® AP).

In preferred compositions at least one organic sunscreen is immobilisedby being coupled to a surface or a polymeric chain, preferably to thesurface of inorganic sunscreen particles and/or a siloxane polymericchain. The coupling of UV filters to surfaces is for example describedin the pending German patent applications DE 10055588.8 and DE10055469.5. According to these patent applications, that are explicitlyincluded by reference in here, the UV filters are coupled via functionalgroups and preferably via spacer groups to an inorganic surface,preferably a silicon or titanium dioxide surface. Also preferred arecompositions that comprise at least one polymeric UV filter. PolymericUV filters are those polymers with UV filtering properties in the mainchain. The chemical attaching of UV filters to polymeric chains,preferably siloxane chains is for example described in EP-A-0709080,EP-A-0982310 and EP-A-0933376. One especially preferred UV filterattached to a siloxan chain is Dimethico-diethyl-benzal-malonate.

In a further preferred embodiment the compositions comprise at least onemicronized organic UV filter, preferably selected from triazinderivatives, benzotriazole derivatives, vinyl group-containing amidederivatives, cinnamic acid amide derivatives and/or sulfonatedbenzimidazole derivatives, most preferred from triazin derivatives.Those micronized organic UV filters are for example described in WO99/66896 and WO 00/78277, included by reference herein. A preferredexample for micronized UV filters is2,2′-methylen-bis-[6-(2H-benztriazol-2-yl)-4-/1,1,3,3-tetramethylbutyl)-phenol(e.g. Tinsorb™ M).

In general all known organic UV filters may be encapulated or immobilzedaccording to our invention. Particular preference is given to those UVfilters whose physiological safety has already been demonstrated. Thereare many tried and tested substances known from the specialistliterature for both UVA and also UVB filters, e.g.

Benzylidenecamphor derivatives, such as

-   -   3-(4′-methylbenzylidene)-dl-camphor (e.g. Eusolex® 6300),    -   3-benzylidenecamphor (e.g. Mexoryl® SD),    -   polymers of N-{(2 and        4)-[(2-oxoborn-3-ylidene)methyl]benzyl}acrylamide (e.g. Mexoryl®        SW),    -   N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)anilinium        methylsulfate (e.g. Mexoryl® SK) or    -   α-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid (e.g. Mexoryl®        SL), benzoyl- or dibenzoylmethanes, such as    -   1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione        (e.g. Eusolex® 9020) or    -   4-isopropyldibenzoylmethane (e.g. Eusolex® 8020), benzophenones,        such as    -   2-hydroxy-4-methoxybenzophenone (e.g. Eusolex® 4360) or    -   2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium        salt (e.g. Uvinul® MS-40),        4,4,-diarylbutadienes as described in EP-A-0 916 335,        methoxycinnamic esters, such as    -   octyl methoxycinnamate (e.g. Eusolex® 2292),    -   isopentyl 4-methoxycinnamate, e.g. as a mixture of the isomers        (e.g. Neo Heliopan® 1000),        salicylate derivatives, such as    -   2-ethylhexyl salicylate (e.g. Eusolex® OS),    -   4-isopropylbenzyl salicylate (e.g. Megasol®) or    -   3,3,5-trimethylcyclohexyl salicylate (e.g. Eusolex® HMS),    -   4-aminobenzoic acid and derivatives, such as    -   4-aminobenzoic acid,    -   2-ethylhexyl 4-(dimethylamino)benzoate (e.g. Eusolex® 6007),    -   ethoxylated ethyl 4-aminobenzoate (e.g. Uvinul® P25),    -   diphenylacrylates, e.g.        2-ethylhexyl-2-cyano-3,3-diphenylacrylate (Eusolex® OCR)        and further substances,such as 2-phenylbenzimidazole-5-sulfonic        acid, and its potassium, sodium and triethanolamine salts (e.g.        Eusolex® 232),        3,3′-(1,4-phenylenedimethylene)-bis(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-ylmethanesulfonic        acid and its salts (e.g. Mexoryl® SX),        2,4,6-trianilino-(p-carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine        (e.g. Uvinul® T 150) and        2-(4-Diethylamino-2-hydroxy-benzoyl)-benzoic acid hexyl ester        (e.g. Uvinul® A Plus, BASF).

The compounds given in the list are only to be regarded as examples. Itis of course also possible to use other UV filters.

Further suitable organic UV filters are, for example,2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol(e.g. Silatrizole®), bis(2-ethylhexyl)4,4′-[(6-[4-((1,1-dimethylethyl)aminocarbonyl)-phenylamino]-1,3,5-triazine-2,4-diyl)diimino]bisbenzoate(e.g. Uvasorb® HEB),α-(trimethylsilyl)-ω-[trimethylsilyl)oxy]poly[oxy(dimethyl [and about 6%methyl[2-[p-[2,2-bis(ethoxycarbonyl]vinyl]phenoxy]-1-methylenethyl] andabout 1.5% methyl[3-[p-[2,2-bis(ethoxycarbonyl)vinyl)phenoxy)propenyl)and 0.1 to 0.4% (methyl-hydrogen]silylene]] (n≈60) (CAS No. 207574-74-1),2,2′-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)(CAS No. 103 597-45-1),2,2′-(1,4-phenylene)bis(1H-benzimidazol-4,6-disulfonic acid, monosodiumsalt) (CAS No. 180 898-37-7) and2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxyl]phenyl}-6(4-methoxy-phenyl)-1,3,5-triazine(CAS No.103 597-45-, 187 393-00-6).

These UV filters are usually incorporated into cosmetic formulations inan amount of from 0.5 to 20% by weight, preferably 1-15%.

Conceivable as inorganic UV filters are those from the group of titaniumdioxides, such as, for example, coated titanium dioxide (e.g. Eusolex®T-2000, Eusolex® T-AQUA), zinc oxides (e.g. Sachtotec®), iron oxides andalso cerium oxides. These inorganic UV filters are generallyincorporated into cosmetic formulations in an amount of from 0.5 to 20%by weight, preferably 2-10%.

Preferred compounds with UV-filtering properties are3-(4′-methylbenzylidene)-dl-camphor,1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione,4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octylmethoxycinnamate, 3,3,5-trimethylcyclohexyl salicylate, 2-ethylhexyl4-(dimethylamino)benzoate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate,2-phenylbenzimidazole-5-sulfonic acid, its potassium, sodium andtriethanolamine salts and coated titanium dioxide.

By combining two or more compounds listed above it is possible tooptimize the protective action against harmful effects of UV radiation.The combination of the above-mentioned UV filters in a formulation givesa composition which combines light protection with particular mildnessto the skin. All of the UV filters specified can be used in encapsulatedor in immobilized form as described above.

It is also preferred, if the composition comprises at least oneinorganic sunscreen agent, preferably at least one microparticulateinorganic sunscreen, most preferably selected from zink or titaniumdioxide.

It is therefore preferred according to the invention if one or more ofthe above-mentioned UV filters are present in encapsulated form. In thisconnection, it is advantageous if the capsules are so small that theycan not be observed with the naked eye. To achieve the above-mentionedeffects, it is also necessary for the capsules to be sufficiently stableand not to release the encapsulated active ingredient (UV filter) intothe surroundings, or to release it only to a slight extent.

Advantages of the compositions according to our invention are:

-   -   High Sun protection factor (SPF).    -   Good photostability of the composition.    -   No or low penetration of the skin

Another embodiment of our invention therefore is the use of sunscreencapsules to prevent sunscreens form penetration of the skin.

The performance of a cosmetic formulation according to the SPF isinfluenced by the distribution of the UV filters on the surface of theskin or within the upper corneocyte layers. Therefore the rheology ofthe formulation is a key issue to increase the SPF (boost effect).According to the theory, applied cosmetic vehicles fill up the furrowseasily while the ridges are not covered efficiently by the formulationsin many cases. A further advantage of the formulations comprisingSunscreen capsules is that they cover both the furrows as well as theridges of the skin which is due to their rheological influence oncosmetic formulations. This enables the formulation to build up a moreuniform layer on top of the skin's surface. Due to this SPF boost effectof sunscreen capsules formulations comprising the sunscreen capsules aresupposed to show a higher SPF value compared to formulations withoutsuch capsules but the same amount of UV filters. Therefore anotherembodiment of our invention is the use of capsules to increase the SPFvalue of a given sunscreen formulation.

The protecting action against oxidative stress or against the effect offree radicals can be further improved if the formulation comprises oneor more antioxidants.

There are many tried and tested substances known from the specialistliterature which can be used, e.g. amino acids (e.g. glycine, histidine,tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanicacid) and derivatives thereof, peptides, such as D,L-carnosine,D-carnosine, L-carnosine and derivatives thereof (e.g. anserine),carotinoids, carotenes (e.g. α-carotene, β-carotene, lycopene) andderivatives thereof, chlorogenic acid and derivatives thereof, lipoicacid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose,propylthiouracil and other thiols (e.g. thioredoxin, glutathione,cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl,propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl,cholesteryl and glycerylesters thereof, and salts thereof, dilaurylthiodipropionate, distearyl thiodipropionate, thiodipropionic acid andderivatives thereof (esters, ethers, peptides, lipids, nucleotides,nucleosides and salts), and sulfoximine compounds (e.g.buthionine-sulfoximine, homocysteine-sulfoximine, buthionine-sulfone,penta-, hexa- and heptathionine-sulfoximine) in very low tolerated doses(e.g. pmol to μmol/kg), and also (metal) chelating agents, (e.g.α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin),α-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid,bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA andderivatives thereof, unsaturated fatty acids and derivatives thereof,vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbylphosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitaminE acetate), vitamin A and derivatives (e.g. vitamin A palmitate), andconiferyl benzoate of benzoin resin, rutin and salts of the sulfuricester of rutin and derivatives thereof, α-glycosyl rutin, ferulic acid,furfurylidineglucitol, carosine, butylhydroxytoluene,butylhydroxyanisol, nordihydroguaretic acid, trihydroxybutyrophenone,quercetin, uric acid and derivatives thereof, mannose and derivativesthereof, zinc and derivatives thereof (e.g. ZnO, ZnSO₄), selenium andderivatives thereof (e.g. selenomethionine), stilbenes and derivativesthereof (e.g. stilbene oxide, trans-stilbene oxide).

Mixtures of antioxidants are likewise suitable for use in the cosmeticformulations according to the invention. Known and commercial mixturesare, for example, mixtures comprising, as active ingredients, lecithin,L-(+)-ascorbyl palmitate and citric acid (e.g. Oxynex® AP), naturaltocopherols, L-(+)-ascorbyl palmitate, L-(+)ascorbic acid and citricacid (e.g. Oxynex® K LIQUID), tocopherol extracts from natural sources,L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (e.g.Oxynex® L LIQUID), DL-α-tocopherol, L-(+)-ascorbyl palmitate, citricacid and lecithin (e.g. Oxynex® LM) or butylhydroxytoluene (BHT),L-(+)-ascorbyl palmitate and citric acid (e.g. Oxynex® 2004).

The formulations according to the invention can comprise vitamins asfurther ingredients. Preferably, vitamins and vitamin derivatives chosenfrom vitamin A, vitamin A propionate, vitamin A palmitate, vitamin Aacetate, retinol, vitamin B, thiamine chloride hydrochloride (vitaminB₁), riboflavin (vitamin B₂) nicotinamide, vitamin C (ascorbic acid),vitamin D, ergocalciferol (vitamin D₂), vitamin E, DL-α-tocopherol,tocopherol E acetate, tocopherol hydrogensuccinate, vitamin K₁, esculin(vitamin P active ingredient), thiamine (vitamin B₁) nicotinic acid(niacin), pyridoxine, pyridoxal, pyridoaxmine, (vitamin B₆),panthothenic acid, biotin, folic acid and cobalamine (vitamin B₁₂) arepresent in the cosmetic formulations according to the invention,particularly preferably vitamin A palmitate, vitamin C, DL-α-tocopherol,tocopherol E acetate, nicotinic acid, panthothenic acid and biotin.

The composition of our invention can be a cosmetic formulation or apharmaceutical formulation.

Examples of application forms of the cosmetic or pharmaceuticalformulations according to the invention which may be mentioned are:solutions, suspensions, emulsions, PIT emulsions, pastes, ointments,gels, creams, lotions, powders, soaps, foams, surfactant-containingcleansing preparations, oils, aerosols and sprays. Examples of otherapplication forms are sticks, shampoos and shower preparations. Anycustomary carriers, auxiliaries and optionally further activeingredients may be added to the formulation.

Preferred auxiliaries originate from the group of preservatives,antioxidants, stabilizers, solubility promoters, vitamins, colorants,odour improvers.

Ointments, pastes, creams and gels may comprise the customary carriers,e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth,cellulose derivatives, polyethylene glycols, silicones, bentonites,silica, talc and zinc oxide or mixtures of these substances.

Powders and sprays may comprise the customary carriers, e.g. lactose,talc, silica, aluminium hydroxide, calcium silicate and polyamide powderor mixtures of these substances. Sprays can additionally comprisecustomary propellants, e.g. chlorofluorocarbons, propane/butane ordimethyl ether.

Solutions and emulsions can comprise the customary carriers, such assolvents, solubility promoters and emulsifiers, e.g. water, ethanol,isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzylbenzoate, propylene glycol, 1,3-butylglycol, oils, in particular cottonseed oil, peanut oil, wheatgerm oil, olive oil, castor oil and sesameoil, glycerol fatty acid ester, polyethylene glycols and fatty acidesters of sorbitan or mixtures of these substances.

Suspensions can comprise the customary carriers such as liquid diluents,e.g. water, ethanol or propylene glycol, suspending agents, e.g.ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters andpolyoxyethylene sorbitan esters, microcrystalline cellulose, aluminiummetahydroxide, bentonite, agar agar and tragacanth or mixtures of thesesubstances.

Soaps can comprise the customary carriers, such as alkali metal salts offatty acids, salts of fatty acid mono esters, fatty acid proteinhydrolysates, isethionates, lanolin, fatty alcohol, vegetable oils,plant extracts, glycerol, sugars or mixtures of these substances.

Surfactant-containing cleansing products can comprise the customarycarrier substances, such as salts of fatty alcohol sulfates, fattyalcohol ether sulfates, sulfosuccinic monoesters, fatty acid proteinhydrolysates, isethionates, imidazolinium derivatives, methyl taurates,sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fattyalcohols, fatty acid glycerides, fatty acid diethanolamides, vegetableand synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acidesters or mixtures of these substances.

Face and body oils can comprise the customary carrier substances such assynthetic oils, such as fatty acid esters, fatty alcohols, siliconeoils, natural oils, such as vegetable oils and oily plant extracts,paraffin oils, lanolin oils or mixtures of these substances.

Further typically cosmetic application forms are also lipsticks, lipcaresticks, mascara, eyeliner, eyeshadow, blusher, powder make-up, emulsionmake-up and wax make-up, and sunscreen, presun and aftersunpreparations.

All compounds or components which can be used in the cosmeticformulations are either known and available commercially or can besynthesized by known processes.

As dispersant or solubilizer it is possible to use an oil, wax or otherfatty substance, a lower monoalcohol or a lower polyol or mixturesthereof. Preferred monoalcohols or polyols include ethanol, isopropanol,propylene glycol, glycerol and sorbitol.

A preferred embodiment of the invention is an emulsion in the form of aprotective cream or milk and which comprise, for example, fattyalcohols, fatty acids, fatty acid esters, in particular triglycerides offatty acids, lanolin, natural and synthetic oils or waxes andemulsifiers in the presence of water.

Further preferred embodiments are oily lotions based on natural orsynthetic oils and waxes, lanolin, fatty acid esters, in particulartriglycerides of fatty acids, or oily-alcoholic lotions based on a loweralcohol, such as ethanol, or a glycerol, such as propylene glycol,and/or a polyol, such as glycerol, and oils, waxes and fatty acidesters, such as triglycerides of fatty acids.

The cosmetic preparation according to the invention can also be in theform of an alcoholic gel which comprises one or more lower alcohols orpolyols, such as ethanol, propylene glycol or glycerol, and a thickener,such as siliceous earth. The oily-alcoholic gels also comprise naturalor synthetic oil or wax.

Preferred compositions of our invention are hydrogels. Thehydrophilicity of the capsule wall can be set independently of thesolubility of the UV filter. For example, it is possible to incorporateeven hydrophobic UV filters into purely aqueous formulations. Due tothis possibility to include high amounts of hydrophobic UV filters inencapsulated or immobilized form, as described above, those hydrogels ofour inventions can posses high SPF values, in a range normally onlyacheived with oily formulations.

The solid sticks consist of natural or synthetic waxes and oils, fattyalcohols, fatty acids, fatty acid esters, lanolin and other fattysubstances.

All compounds or components which can be used in the cosmetic orpharmaceutical formulations are either known and available commerciallyor can be synthesized by known processes.

The composition according to the invention is particularly suitable forprotecting human skin against the harmful influences of the UVconstituents in sunlight, in addition they also offer protection againstageing processes of the skin and against oxidative stress, i.e. againstdamage caused by free radicals, as are produced, for example, by solarirradiation, heat or other influences.

Therefore the use of a composition according to our invention for themanufacture of a medicament suitable for the prophylaxis of damages ofthe skin caused by sunray, especially for the prophylaxis of sunburn andsun-caused erythrema is another embodiment of our invention. A furtherembodiment is the cosmetic prophylaxis of damages of the skin caused bysunray, especially for the prophylaxis of sunburn and sun-causederythrema.

The formulation may comprise adjuvants which are customarily used inthis type of composition, such as, for example, thickeners, softeners,moisturizers, surface-active agents, emulsifiers, preservatives,perfumes, waxes, lanolin, propellants, dyes and/or pigments which colourthe composition itself or the skin, and other ingredients customarilyused in cosmetics.

The composition may be a foamable composition able to be foamed up withor without an propellant. According to our invention it is especiallypreferred if the foam is produced without the use of a organicpropellant. Sprays using organic propellents may not be stored in directsun or at higher temperatures; conditions that for example can often befound on the beach during summer. An advantage of preferred compositionsaccording to our invention is that the may be stored and used even underthese conditions.

Preferred compositions are included in a foam dispenser, preferably in afoam dispenser that requires no organic propellant as described above.

As foam builders/stabilisers in general all substances able to build orstabilise a foam may be used. Those substances in general are known tothose skilled in the art. Preferred foam builders/stabilisers are thosewhich are skin tolerant or even more preferably give a benefit to theskin.

The foam builders/stabilisers are usually present in an amount of about0.01 to 20% by weight, preferably in an amount of 0.1 to 5% by weightand even more preferred in an amount of 0.1 to 3% by weight.

Preferred foam builders/stabilisers are cetyl phosphate, DEA cetylphosphate, TEA myristate, TEA stearate, magnesium stearate, sodiumstearate, potassium laurate, potassium ricinoleate, sodium cocoate,sodium tallowate, potassium castorate, sodium oleate and mixturesthereof.

Other preferred foam stabilisers are so called foam boosters. Foamboosters are substances which increase the surface viscosity of theliquid which surrounds the individual bubbles in a foam. These agentsare commonly used in shaving soaps, shampoos, bubble baths, liquidsoaps, mousses, or aerosol-dispensed foams. Also Film Formers orViscosity-Increasing Agents maybe used as foam boosters. The listingbelow gives examples for foam boosters which can also be classified assurfactants (INCI names):

Acetamide MEA, Almondamide DEA, Almondamidopropylamine Oxide,Almondamidopropyl Betaine, Apricotamide DEA, Apricotamidopropyl Betaine,Avocadamide DEA, Avocadamidopropyl Betaine, Babassuamide DEA,Babassuamidopropylamine Oxide, Babassuamidopropyl Betaine, BehenamideDEA, Behenamide MEA, Behenamidopropyl Betaine, Behenamine Oxide, BehenylBetaine, Canolamidopropyl Betaine, Capramide DEA, Carnitine, CetearylAlcohol, Cetyl Alcohol, Cetyl Betaine, Cocamide DEA, Cocamide MEA,Cocamide MIPA, Cocamidoethyl Betaine, Cocamidopropylamine Oxide,Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Cocamine Oxide,Cocoamphodipropionic Acid, Cocobetainamido Amphopropionate,Coco-Betaine, Coco-Hydroxysultaine, Coco-Morpholine Oxide, CoconutAlcohol, Coco/Oleamidopropyl Betaine, Coco-Sultaine, CocoylSarcosinamide DEA, DEA-Cocoamphodipropionate, DEA-Lauraminopropionate,Decyl Alcohol, Decylamine Oxide, Decyl Betaine, DiethanolaminooleamideDEA, Dihydroxyethyl C8-10 Alkoxypropylamine Oxide, Dihydroxyethyl C9-11Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylaminde Oxide,Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide,Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tallowamine Oxide,Dimethicone Propyl PG-Betaine, Disodium Caproamphodiacetate, DisodiumCaproamphodipropiante, Disodium Capryloamphodiacetate, DisodiumCapryloamphodipropionate, Disodium Cetearyl SulfosuccinateDisodiumCocamido MIPA-Sulfosuccinate, Disodium Cocamido PEG-3 Sulfosuccinate,Disodium Cocaminopropyl Iminodiacetate,DisodiumCocoamphocarboxyethylhydroxypropylsulfonate, DisodiumCocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium C12-15Pareth Sulfosuccinate, Disodium Deceth-5 Sulfosuccinate, DisodiumDeceth-6 Sulfosuccinate, Disodium Hydrogenated Cottonseed GlycerideSulfosuccinate, Disodium Isodecyl Sulfosuccinate, Disodium IsostearamidoMEA-Sulfosuccinate, Disodium Isostearamido MlPA-Sulfosuccinate, DisodiumIsostearoamphodiacetate, Disodium Isostearoamphodipropionate, DisodiumIsostearyl Sulfosuccinate, Disodium Laneth-5 Sulfosuccinate, DisodiumLauramido MEA-Sulfosuccinate, Disodium Lauramido PEG-2 Sulfosuccinate,Disodium Laureth-5 Carboxyamphodiacetate, Disodium LaurethSulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, DisodiumLauroamphodiacetate, Disodium Lauroamphodipropiante, Disodium LaurylSulfosuccinate, Disodium Myristamido MEA-Sulfosuccinate, DisodiumNonoxynol-10 Sulfosuccinate, Disodium Oleamido MEA-Sulfosuccinate,Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2Sulfosuccinate, Disodium Oleoamphodipropionate, Disodium Oleth-3Sulfosuccinate, Disodium Oleyl Sulfosuccinate, Disodium PalmitamidoPEG-2 Sulfosuccinate, Disodium Palmitoleamido PEG-2 Sulfosuccinate,Disodium PEG4 Cocamido MIPA-Sulfosuccinate, Disodium PPG-2-Isodeceth-7Carboxyamphodiacetate, Disodium Ricinoleamido MEA-Sulfosuccinate,Disodium Stearamido MEA-Sulfosuccinate, Disodium Stearoamphodiacetate,Disodium Stearyl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate,Disodium Tallamido MEA-Sulfosuccinate, Disodium TallowamidoMEA-Sulfosuccinate, Disodium Tallowamphodiacetate, Disodium TallowSulfosuccinamate, Disodium Tridecylsulfosuccinate, DisodiumUndecylenamido MEA-Sulfosuccinate, Disodium Undecylenamido PEG-2Sulfosuccinate, Disodium Wheat Germamido MEA-Sulfosuccinate, DisodiumWheat Germamido PEG-2 Sulfosuccinate, Disodium Wheatgermamphodiacetate,Di-TEA-Oleamido PEG-2 Sulfosuccinate, Ditridecyl Sodium Sulfosuccinate,Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Alcohol,Hydrogenated Tallowamide DEA, Hydrogenated Tallowamine Oxide,Hydrogenated Tallow Betaine, Hydroxyethyl CarboxymethylCocamidopropylamine, Hydroxyethly Hydroxypropyl C12-15 AlkoxypropylamineOxide, Hydroxystearamide MEA, Isostearamide DEA, Isostearamide MEA,Isostearamide MIPA, Isostearamidopropylamine Oxide, IsostearamidopropylBetaine, Isostearamidopropyl Morpholine Oxide, Lactamide MEA,Lanolinamide DEA, Lauramide DEA, Lauramide MEA, Lauramide MIPA,Lauramide/Myristamide DEA, Lauramidopropylamine Oxide, LauramidopropylBetaine, Lauramine Oxide, Lauroamphodipropionic Acid, Lauryl Alcohol,Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, LecithinamideDEA, Linoleamide DEA, Linoleamide MEA, Linoleamide MIPA, MethylMorpholine Oxide, Minkamide DEA, Minkamidopropylamine Oxide,Minkamidopropyl Betaine, Myristamide DEA, Myristamide MEA, MyristamideMIPA, Myristamidopropylamine Oxide, Myristamidopropyl Betaine,Myristamine Oxide, Myristaminopropionic Acid, Myristyl Alcohol, MyristylBetaine, Myristyl/Cetyl Amine Oxide, Oleamide DEA, Oleamide MEA,Oleamide MIPA, Oleamidopropylamine Oxide, Oleamidopropyl Betaine,Oleamidopropyl Hydroxysultaine, Oleamine Oxide, Oleyl Betaine, OlivamideDEA, Olivamidopropylamine Oxide, Olivamidopropyl Betaine, Palmamide DEA,Palmamide MEA, Palmamide MIPA, Palmamidopropyl Betaine, Palmitamide DEA,Palmitamide MEA, Palmitamidopropylamine Oxide, PalmitamidopropylBetaine, Palmitamine Oxide, Palm Kernel Alcohol, Palm Kernelamide DEA,Palm Kernelamide MEA, Palm Kernelamide MIPA, Palm KernelamidopropylBetaine, Peanutamide MEA, Peanutamide MIPA, PEG-3 Cocamide, PEG-2Hydrogenated Tallow Amine, PEG-3 Lauramide, PEG-3 Lauramide Oxide, PEG-2Oleamide, PEG-3 Oleamide, PEG-2 Oleamine, PEG-2 Soyamine, PEG-2Stearamine, Potassium Dihydroxyethyl Cocamine Oxide Phosphate,Ricinoleamide DEA, Ricinoleamide MEA, Ricinoleamide MIPA,Ricinoleamidopropyl Betaine, Sesamide DEA, Sesamidopropylamine Oxide,Sesamidopropyl Betaine, Sodium Caproamphoacetate, SodiumCaproamphohydroxy-propylsulfonate, Sodium Caproamphopropionate, SodiumCapryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, SodiumCapryloamphoproprionate, Sodium Cocoamphoacetate, SodiumCocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, SodiumCornamphopropionate, Sodium Isostearoampho-acetate, SodiumIsostearoamphopropionate, Sodium Lauramidopropyl Hydroxyphostaine,Sodium Lauraminopropionate, Sodium Lauriminodipropionate, SodiumLauroamphoacetate, Sodium/MEA Laureth-2 Sulfosuccinate, SodiumMyristoamphoacetate, Sodium Oleoamphoacetate, SodiumOleoamphohydroxy-propylsulfonate, Sodium Oleoamphopropionate, SodiumRicinoleoamphoacetate, Sodium Stearoamphoacetate, SodiumStearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, SodiumTallamphopropionate, Sodium Tallowamphoacetate, Sodium Tallowate, SodiumUndecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium WheatGermamphoacetate, Soyamide DEA, Soyamidopropyl Betaine, Stearamide AMP,Stearamide DEA, Stearamide DEA-Distearate, Stearamide MEA, StearamideMEA-Stearate, Stearamide MIPA, Stearamidopropylamine Oxide,Stearamidopropyl Betaine, Stearamine Oxide, Stearyl Alcohol, StearylBetaine, Tallamide DEA, Tallowamide DEA, Tallowamide MEA,Tallowamidopropylamine Oxide, Tallowamidopropyl Betaine,Tallowamidopropyl Hydroxysultaine, Tallowamine Oxide, Tallow Betaine,TEA-Lauraminopropionate, TEA-Myristaminopropionate, Trideceth-2Carboxamide MEA, Trisodium Lauroampho PG-Acetate Phosphate Chloride,Undecylenamide DEA, Undecylenamide MEA, Undecylenamidopropylamine Oxide,Undecylenamidopropyl Betaine, Wheat Germamide DEA, WheatGermamidopropylamine Oxide, Wheat Germamidopropyl Betaine.

In another embodiment at least one foam builder/stabiliser is selectedfrom foaming surfactants, preferably from alkylglyosides, anionicprotein derivatives or fatty acid sulfonates.

An especially preferred foam builder/stabilisers are anionic proteinderivatives, such as lipoaminoacids described in WO 98/09611, WO99/27902 and WO 99/45899. Most preferred under these anionic proteinderivatives are sodium lauroyl oat amino acids, for example known asProteol™ Oat (Tradename of Seppic).

The cosmetic formulation can also be used to protect the hair againstphotochemical damage in order to prevent changes of colour shades,decoloration or damage of a mechanical nature. In this case, a suitableformulation is in the form of a shampoo or lotion for rinsing out, theformulation in question being applied before or after shampooing, beforeor after colouring or bleaching or before or after permanent waving. Itis also possible to choose a formulation in the form of a lotion or gelfor styling or treating the hair, in the form of a lotion or gel forbrushing or blow-waving, in the form of a hair lacquer, permanent wavingcomposition, colorant or bleach for the hair. The cosmetic formulationmay comprise various adjuvants used in this type of composition, such assurface-active agents, thickeners, polymers, softeners, preservatives,foam stabilizers, electrolytes, organic solvents, silicone derivatives,antigrease agents, dyes and/or pigments which colour the compositionitself or the hair, or other ingredients customarily used for hair care.

To protect the skin and/or natural or sensitized hair against solarrays, the cosmetic composition is applied to the skin or the hair.Sensitized hair is understood here as meaning hair which has beensubjected to a chemical treatment, such as a permanent waving treatment,a colouring process or bleaching process.

The compositions of our invention can be produced by by mixingdispersions of insuloble and/or encapsulated sunscreens and/ordispersions of inorganic sunscreen particles with other ingredients ofthe composition.

The examples below illustrate the present invention in more detailwithout limiting the scope of the invention. The following trade namesare used in the example formulations:

EXAMPLES

The silica capsules used in the examples (Eusolexo® UV-Pearls™) areobtained by a sol-gel process, as is described in the applications WO00/09652, WO 00/72806 and WO 00/71084. The preparation of correspondingcapsules is known to the person skilled in the art, for example, fromthe cited patent applications, the contents of which also expresslybelonging to the subject-matter of the present application.

UV Pearls™ in the examples means an aqueous dispersion of silicacapsules comprising about 33% by weight of UV filters.

Abbreviations:

-   BMDBM butyl methoxydibenzoylmethane-   BP-3 benzophenone-3-   OCR 2-ethylhexyl-2-cyano-3,3-diphenylacrylate-   OMC octyl methoxycinnamate

Example 1

Photo-acoustic in vivo Investigation of the Stratum Corneum

Method

The photo-acoustic method (Puccetti G, Leblanc R M: Photoacousticspectroscopy of sunscreens applied to human skin: Towards the in situmonitoring of filter penetration and interaction in the different layersof the skin. Recent Res. Devel. Photochem. & Photobiol, 5: 79-93 (2001);Imhof R E, Whitters C J, Birch D J S: Opto-thermal in vivo monitoring ofsunscreens on skin. Phys. Med. Biol., 35: 95-102 (1990); Giese K,Nicolaus A, Sennhenn B, Külmel K: Photoacoustic in vivo study of thepenetration of sunscreens into human skin. Can. J. Phys., 64: 1139-1141(1986)) is based on a widespread phenomenon: light absorbed by amaterial is partly re-emitted as heat. Energy from a light source istransferred to a sample via light absorption and partially re-emitted asheat, which is then detected by a sensor. Under pulsed light conditions(e.g. laser), a sample will generate a pulse of heat release.

Human skin absorbs light in the UV range, which is therefore used assource of light. Typical photo-acoustic studies involve near surfacedetection, i.e. typically 40-60 μm, within the limits of the maximalheat diffusion depth in skin.

The dermal uptake of a product applied to skin is assessed usingphoto-acoustics by monitoring the amplitude of the heat response. In thecase of product applications to skin, molecules entering the skin areindicated by a decrease in the photo-acoustic heat response. This is dueto the diffusion of molecules through the stratum corneum barrier layerand towards skin layers beyond 40-60 μm.

The dermal uptake of two formulations containing OMC (see Table 1) ismeasured after application to the forearm of a volunteer. The study isperformed at two wavelengths of light: 266 nm to monitor the OMC (lightis absorbed by OMC mostly) and 355 nm to observe formulation effects(light is mostly absorbed by the skin background). Energies of lightirradiation are kept below erythema levels, at 0.8 mJ/cm² for 355 nm and0.4 mJ/cm² for 266 nm.

Table 1: O/W lotion applied in vivo to human skin volunteers forphoto-acoustic measurement of the skin. Both formulations contain 7% ofOMC but one with free OMC, and the other as Eusolex® UV-Pearls™ OMC.

Free OMC Eusolex ® UV-Pearls ™ CTFA/INCl % (w/w) % (w/w) Ethylhexylmethoxycinnamate, 7.00 — BHT Isopropyl myristate 4.00 4.00 C12-15 Alkylbenzoate 4.00 4.00 Cetyl alcohol 1.50 1.50 Steareth-2 2.00 2.00Steareth-21 2.50 2.50 Dimethicone 0.50 0.50 Aqua (water) 77.07  63.77 Carbomer 0.20 0.20 Eusolex ® UV-Pearls ™ OMC — 20.03  Triethanolamine0.23 0.23 Phenoxyethanol, isopropylparaben, 1.00 1.00isobutylparaben,butylparaben

The irradiation surface is 3×3 mm. Products are applied under identicalconditions: 20 mg are spread over a circular area of 5 cm in diameter(˜1 mg/cm²). Data are the result of 3 experiments carried out underidentical conditions, at 24 h intervals, on the forearm of a volunteer.

Results

The results show classical penetration dynamics for non-encapsulated OMC(FIG. 1). A regular signal decrease is observed at 266 nm over 2 hours,which reaches the signal value of skin without OMC. On the contrary,encapsulated OMC shows a short-term decrease (over 30 min), followed byan increase and subsequent stabilization at 90 min. This increase iscontrary to penetration dynamics and indicates stable light absorption.Results at 355 nm confirm the surface presence of encapsulated OMC byreaching a long-term signal clearly higher than skin and characteristicof a permanent residue. Finally, the high photo-acoustic response ofencapsulated OMC around 90-120 min confirms efficient UV absorption ofthe Eusolex® UV-Pearls™ and their excellent stability.

A comparison of OMC with Eusolex® UV-Pearls™ OMC shows a clearlydifferent behavior on skin for the latter, opposite to classicalpenetration kinetics. While short-term formulation effects are observedfor both products, the UV pearls show a signal increase for longerperiods, which is typical of surface deposits.

Conclusion

In comparison to free UV filters, Eusolex® UV-Pearls™ have:

-   -   A high and stable long-term photo-acoustic response leading to        high UV absorption    -   A long-term photo-acoustic response clearly higher than the skin        (and formulation) representing surface presence of the Eusolex®        UV-Pearls™ while non-encapsulated OMC has a significantly higher        potential to enter the skin.

Example 2

Differential Stripping of the Stratum Corneum

The goal of this study was to determine and compare the distribution ofOMC in the stratum corneum of two different formulations as applied toporcine skin, which serves as a model for in vivo human skinapplications. The method used has been established (Weigmann H-J,Lademann J, Meffert H, Schaefer H, Sterry W: Determination of the hornylayer profile by tape stripping in combination with optical spectroscopyin the visible range as a prerequisite to quantify percutaneousabsorption. Skin Pharmacol Appl Skin Physiol, 12:34-45 (1999)) and isdescribed below. This method is based on conventional strippingprocedures combined with UV/VIS spectroscopy to determine both thesubstance, to be analyzed, and, in parallel, the weight of thecomeocytes. This since it is possible to obtain the complete stratumcorneum with this stripping procedure, the strips thus can be shown as ahorny layer profile.

Method

Porcine ear skin is used due to its availability and well-knownsimilarity to human skin. The horny layer had a thickness of about 20μm. Two formulations are applied to an area of 20 cm² with aconcentration of 2 mg/cm² (200 μg OMC/cm²) and exposed for one hour.Both formulations contain 10% OMC but one with free OMC, and the otheras Eusolex® UV-Pearls™ OMC (see Table 2). Afterwards, topicalapplication and stripping was carried out using a standard procedure(The emulsion is applied with a syringe and evenly distributed with agloved finger. After pressure application, all strips were removed fromthe marked area). The stripping is repeated as long as the spectralphotometer has a transmission of 99.8% compared to the original tapestrip as reference.

TABLE 2 Formulations applied to porcine skin for a comparativedifferential stripping experiment. Both formulations contain 10% OMC butone with free OMC, and the other as Eusolex ® UV-Pearls ™ OMC. Free OMCEusolex ® UV-Pearls ™ CTFA/INCl % (w/w) % (w/w) Phase A Ethylhexylmethoxycinnamate, 10.00  — BHT Steareth-10, Steareth-7, 3.50 3.50stearyl alcohol Glyceryl stearate, Ceteth-20 3.00 3.00 Glyceryl stearate3.00 3.00 Microwax 1.50 1.50 Oleoyl oleate 3.50 5.00 Cetearyl octanoate8.00 16.00  Caprylic/Capric triglyceride 4.00 4.50 Propylparaben 0.050.05 Phase B Propylene glycol 4.00 4.00 Allantoin 0.20 0.20 Aqua (water)59.10  29.42  Methylparaben 0.15 0.15 Phase C Eusolex ® UV-Pearls ™ OMC— 29.68 

After evaluation of the amount of stratum corneum photometrically at 900nm, the strips are extracted with methanol, centrifuged and decanted.Amounts of OMC concentrations are calculated from the ratio peak area ofthe OMC to an internal OMC calibration curve. The detection limit forOMC is found to be 1 μg/ml±5%. The experiments are carried out induplicate.

Results

Non-particulate substances lying in the furrows are distributed evenlydue to the applied pressure—this releases the substances from thefurrows, while particulate substances often remain. The differentialstripping method with particles result more in a distribution profile onthe skin than a profile in the stratum corneum (Amadine Amenc:Comparison of the penetraion of organic and inorganic UV filters used insunscreens into the stratum corneum by applying the tape strippingmethod. Diploma-thesis, Ecole Nationale Supérieure de Chimie de Paris,and University Hospital Charité, Department of Dermatology and Allergy,Berlin, Germany (2001)); this has to be taken into account.

Both applied emulsions contain the same amount of UV filter, which hasbeen confirmed by a very good total recovery of the applied 200 μg/cm².FIG. 2 shows the distribution profile in the outermost surface layers ofthe epidermal stratum corneum (SC). In the first strip, nearly 50% ofthe applied OMC is stripped off. After 10 strips, no further Eusolex®UV-Pearls™ OMC can be determined. At this stage, 25% of the SC arestripped off. This corresponds to a maximum depth of 5 μm where the OMCcan be detected. We assume that the data given here for the Eusolex®UV-Pearls™ OMC are higher than reality due to the furrows of the skin.

However, on comparing these data with the free OMC (FIG. 3), we are ableto determine significant differences within the first strips. Free OMCis distributed in the SC up to a depth of 15 μm (which corresponds to75% of the SC and 1 μg/cm² in this strip).

Conclusion

Compared to free filters, Eusolex® UV-Pearls™ significantly reduce theuptake of UV filters by the skin. The encapsulated UV filterspredominantly remain on the surface of the skin.

Example 3

Comparative Release Through an Inert Lipophilic Membrane

The goal of this study is to determine and compare the release of OMCfrom two different formulations through an inert lipophilic membranewhich serves as a model (Jiang R, Benson H A E, Cross S E, Roberts M S.In vitro human epidermal and polyethylene membrane penetration andretention of sunscreen benzophenone-3 from a range of solvents. Pharm.Res., 15: 1863-1886 (1998)) for in vitro human skin applications. (JiangR, Robert M S, Prankerd R J, Benson H A E. Percutaneous absorption ofsunscreen agents from liquid paraffin: self-association of octylsalicylate and effects on skin flux. J. Pharm. Sci., 86: 791-796 (1997);Shah et al: In vitro release from corticosteorid ointments. J. Pham.Sci., 84(9): 1139-1140 (1995); Jiang R, Robert M S, Prankerd R J, BensonH A E. Percutaneous absorption of sunscreen agents from liquid paraffin:self-association of octyl salicylate and effects on skin flux. J. Pharm.Sci., 86: 791-796 (1997)).

Method

Two formulations are prepared, one with free, the other withencapsulated OMC. Both contained the same amount of OMC (see Table 3).

TABLE 3 Emulsion used for the comparative release experiment through aninert lipophilic membrane. Free OMC Eusolex ® UV-Pearls ™ CTFA/INCl %(w/w) % (w/w) Phase A Cetyl dimethicone copolyol 2.2 3.0 Isohexadecane6.8 9.5 Cetearyl isononate 5.6 7.75 Octyl stearate 5.6 7.75 Ethylhexylmethoxycinnamate 8.8 — Phase B Sodium chloride 1.0 1.0 Glycerol 4.0 4.0Eusolex ® UV-Pearls ™ OMC — 25.0 Aqua (water) 66.0  42.0

Tuffryn® membranes (200 nm in pore size) are soaked for 30 minutes inisopropyl myristate and blotted dry with tissue paper prior to use. Thepre-treated membranes are mounted on a horizontal Franz diffusion cellwith an application area of 1.3 cm². The receptor cell contains ca. 3.5ml of phosphate-buffered saline (PBS), pH 7.4, 35° C., and 4% (w/v)bovine serum albumin. The receptor phase is continuously stirred withTeflon-coated magnets.

Each of the two formulations is applied to 3 separate cells,non-occluded, with a finite dose concentration of 5 mg/cm² (572 μgOMC/cell). The emulsions are gently spread over the entire surface ofthe membrane. The duration of the examination is 6 hours, 200 μl of thereceptor phase is removed at specific points of time and replaced withan equal volume of fresh solution at each sampling.

Analysis is by HPLC, OMC concentrations are calculated from the ratiopeak area of the OMC to an internal standard and calibration curve.

Results

FIG. 4 shows a significant difference in the diffusion rate through thehydrophobic membrane of the two formulations. After 6 hours, 72 μg reachthe receptor cell, corresponding to 12.5% of the applied amount (solidline).

In contrast, in the formulation containing Eusolex® UV-Pearls™ OMC, only5.5 μg reach the receptor phase. This means that 98.94% of the appliedUV filter remains on top of the membrane after 6 hours and showed nosignificant penetration. However, very small quantities may have passedthe membrane since the pore size is 200 nm and we have also observedUV-Pearls™ with that small size with e.g. TEM.

Conclusion

Compared to free UV filters, Eusolex® UV-Pearls™ significantly reducethe diffusion of UV filters through a membrane that serves as a modelfor human skin. Encapsulated UV filters remain on top of the membrane.

Example 4

Epidermal Uptake of UV Filters by Human Epidermis

The goal of this study is to determine and compare both the release ofOMC from two different formulations through human epidermal membranesand the epidermal uptake of OMC.

Method

Human female abdominal skin is used to heat-separate the epidermis fromthe dermis. The epidermal membranes thus obtained are mounted onto aFranz diffusion cell. The receptor cell contains PBS and 4% (w/v) bovineserum albumin, resulting in a pH of 7.4. The temperature is set to 35°C. Each of the two formulations is applied to 3 cells, non-occluded,with a finite dose concentration of 5 mg/cm² (572 μg OMC/cell). Theformulations (see Table 3) contain either 8.8% free OMC or 8.8% OMCencapsulated in Eusolex® UV-Pearls™. The duration of examination is 6hours, 200 μl of the receptor phase is removed at specific points oftime and analyzed by HPLC. To analyze the epidermal uptake, theremaining formulation is wiped from the surface of the epidermis withalcohol-soaked tissue and the skin is stripped once with adhesive tape,which is then discarded. A circular punch is used to remove a constantarea of epidermis exposed to the formulations. After extraction, OMCconcentrations are analyzed by HPLC.

Results

Both formulations, one with free formulated OMC, the other withUV-Pearls™, show no significant amount of UV filter penetrating theepidermis.

Regarding the epidermal uptake or substantivity to the epidermal layers,significant differences between the encapsulated and free OMC areobserved (FIG. 5): 3.3 μg of free formulated OMC is collected per mg ofepidermal tissue, while only one third of this was found (1.1. μg/mgtissue) if the OMC is encapsulated in Eusolex® UV-Pearls™.

Compared to free UV filters, Eusolex® UV-Pearls™ significantly reducethe uptake of UV filters by heat-separated human epidermis. Free OMC isabsorbed by the epidermis 3-fold compared to Eusolex® UV-Pearls™.

Example 5

Sun Protection Spray-Mousse

% by supplier weight PHASE A Water, Titanium dioxide, Alumina, sodium 116.5 metaphosphate, phenoxyethanol, sodium methyl paraben (Eusolex ™ Taqua) PHASE B Phenyl benzimidazole Sulfonic Acid (Eusolex ™ 232) 1 3Sodium hydroxyde 1 0.44 Water 10 PHASE C Cl 77891 (Titanium dioxide),Mica, Silica (Timiron ™ 1 1 Splendid gold) Sodium Lauroyl OAT Aminoacids(Proteol ™ oat) 2 5 Dimethicone Copolyol Phosphate (Pecosil ™ PS 100) 20.5 Disodium EDTA 1 0.1 Chlorphenesin 1 0.3 Glycerol 1 3 Water,demineralized Qsp 100 PHASE D silica capsules OMC Octylmethoxycinnamate:42% 1 23Procedure:

Phase A is dispersed in the Phase C. Then phase B and phase D are addedand neutralized at pH=8.

Suppliers: 1 Merck

-   -   2 Seppic

Example 6

Sun Protection Spray-mousse

% by supplier weight PHASE A Water, Titanium dioxide, Alumina, sodium 116 metaphosphate, phenoxyethanol, sodium methyl paraben (Eusolex ™ Taqua) PHASE B Sodium Lauroyl OAT Aminoacids (Proteol ™ oat) 2 5 DisodiumEDTA 1 0.1 Chlorphenesin 1 0.3 Glycerol 1 3 Water, demineralized Qsp 100PHASE C silica capsules OMC (Octylmethoxycinnamate: 42%) 1 23Phase B is dispersed in the Phase A. Then phase C is added andneutralized at pH=5,5. (Suppliers: 1: Merck, 2: Seppic)

Example 7

Sun Protection Spray-mousse

% supplier by weight PHASE A Water, Titanium dioxide, Alumina, sodium 116.5 metaphosphate, phenoxyethanol, sodium methyl paraben (Eusolex ™ Taqua) PHASE B Phenyl benzimidazole Sulfonic Acid (Eusolex ™ 1 3 232)Sodium hydroxyde 1 0.44 Water 10 PHASE C Sodium Lauroyl OAT Aminoacids(Proteol ™ oat) 2 5 Disodium EDTA 1 0.1 Chlorphenesin 1 0.3 Glycerol 1 3Water, demineralized Qsp 100 PHASE D silica capsules OMC(Octylmethoxycinnamate: 1 23 42%)Procedure:

Phase A is dispersed in the Phase C. Then phase B and phase D are addedand neutralized at pH=8.

Suppliers: 1 Merck

-   -   2 Seppic

The average SPC (3 measurements), measured for a layer of 2 mg/cm² onTranspore™ Tape (trademark of 3M) 20 min after application, is 22,4.

Example 8

Eusolex ™ T aqua 16.5 Eusolex ™ 232 3 Eusolex ™ 9020 in silica capsule23 Sodium hydroxyde 0.44 Proteol ™ oat 5 Disodium EDTA 0.1Chlorphenesin1 0.3 Glycerol 3 Water, demineralized Qsp 100

Example 9

Eusolex ™ T aqua 16.5 Eusolex ™ 232 3 Eusolex ™ 6300 in silica capsule20 Sodium hydroxyde 0.44 Proteol ™ oat 5 Disodium EDTA 0.1Chlorphenesin1 0.3 Glycerol 3 Water, demineralized Qsp 100

Example 10

Eusolex ™ T aqua 16.5 Eusolex ™ 232 3 Eusolex ™ OCR in silica capsule 12Eusolex ™ 9020 in silica capsule 12 Sodium hydroxyde 0.44 Proteol ™ oat5 Disodium EDTA 0.1 Chlorphenesin1 0.3 Glycerol 3 Water, demineralizedQsp 100

Example 11

Eusolex ™ T aqua 16.5 Eusolex ™ 232 3 Eusolex ™ 9020/OCR in silicacapsule 12 Eusolex ™ 6300 in silica capsule 12 Sodium hydroxyde 0.44Proteol ™ oat 5 Disodium EDTA 0.1 Chlorphenesin1 0.3 Glycerol 3 Water,demineralized Qsp 100

Example 12

Eusolex ™ T-2000 12 Eusolex ™ 232 3 Eusolex ™ 9020 in silica capsule 12Sodium hydroxyde 0.44 Proteol ™ oat 5 Disodium EDTA 0.1 Chlorphenesin10.3 Glycerol 3 Water, demineralized Qsp 100

TABLE 4 Water-in-oil sunscreen emulsions—values in % (weight/weight) 4-14-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 Titanium dioxide 2 5 3 Benzylidenemalonate 1 2 1 1 polysiloxane Methylene Bis-Benztriazolyl 1 2 1Tetramethylbutylphenol Zinc oxide 5 2 UV-Pearl, OMC 30 15 15 15 15 15 1515 15 15 Polyglyceryl-3-Dimerate 3 3 3 3 3 3 3 3 3 3 Cera Alba 0.3 0.30.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Hydrogenated Castor Oil 0.2 0.2 0.2 0.20.2 0.2 0.2 0.2 0.2 0.2 Paraffinium Liquidum 7 7 7 7 7 7 7 7 7 7Caprylic/Capric Triglyceride 7 7 7 7 7 7 7 7 7 7 Hexyl Laurate 4 4 4 4 44 4 4 4 4 PVP/Eicosene Copolymer 2 2 2 2 2 2 2 2 2 2 Propylene Glycol 44 4 4 4 4 4 4 4 4 Magnesium Sulfate 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.60.6 Tocopherol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 TocopherylAcetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Cyclomethicone 0.5 0.50.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Propylparabene 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 0.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 0.15 0.15 Water ad ad ad ad ad ad ad ad ad ad 100 100 100 100100 100 100 100 100 100 4-11 4-12 4-13 4-14 4-15 4-16 4-17 4-18 Titaniumdioxide 3 2 2 5 Benzylidene malonate polysiloxane 1 0.5 MethyleneBis-Benztriazolyl 1 1 0.5 Tetramethylbutylphenol Zinc oxide 2 UV-Pearl,OMC 15 15 15 30 30 30 15 15 Polyglyceryl-3-Dimerate 3 3 3 3 Cera Alba0.3 0.3 0.3 0.3 2 2 2 2 Hydrogenated Castor Oil 0.2 0.2 0.2 0.2Paraffinium Liquidum 7 7 7 7 Caprylic/Capric Triglyceride 7 7 7 7 HexylLaurate 4 4 4 4 PVP/Eicosene Copolymer 2 2 2 2 Propylene Glycol 4 4 4 4Magnesium Sulfate 0.6 0.6 0.6 0.6 Tocopherol 0.5 0.5 0.5 0.5 TocopherylAcetate 0.5 0.5 0.5 0.5 1 1 1 1 Cyclomethicone 0.5 0.5 0.5 0.5Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methylparabene0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Dicocoyl Pentyerythrityl Citrate(and) 6 6 6 6 Sorbitan Sesquioleate (and) Cera Alba (and) AluminiumStearate PEG-7 Hydrogenated Castor Oil 1 1 1 1 Zinc Stearate 2 2 2 2Oleyl Erucate 6 6 6 6 Decyl Oleate 6 6 6 6 Dimethicone 5 5 5 5Tromethamine 1 1 1 1 Glycerin 5 5 5 5 Allantoin 0.2 0.2 0.2 0.2 water adad ad ad ad ad ad ad 100 100 100 100 100 100 100 100 4-19 4-20 4-21 4-224-23 4-24 4-25 4-26 4-27 4-28 Titanium dioxide 3 3 2 Benzylidenemalonate polysiloxane 1 2 1 1 1 0.5 Methylene Bis-Benztriazolyl 2 1 1 10.5 Tetramethylbutylphenol Zinc oxide 5 2 2 UV-Pearl, OMC 15 15 15 15 1515 15 15 15 10 UV-Pearl, OCR 10 UV-Pearl, OCR, BMDBM 10Polyglyceryl-3-Dimerate 3 Cera Alba 2 2 2 2 2 2 2 2 2 0.3 HydrogenatedCastor Oil 0.2 Paraffinium Liquidum 7 Caprylic/Capric Triglyceride 7Hexyl Laurate 4 PVP/Eicosene Copolymer 2 Propylene Glycol 4 MagnesiumSulfate 0.6 Tocopherol 0.5 Tocopheryl Acetate 1 1 1 1 1 1 1 1 1 0.5Cyclomethicone 0.5 Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 Dicocoyl Pentyerythrityl Citrate, 6 6 6 6 6 6 6 6 6 SorbitanSesquioleate, Cera Alba, Aluminium Stearate PEG-7 Hydrogenated CastorOil 1 1 1 1 1 1 1 1 1 Zinc Stearate 2 2 2 2 2 2 2 2 2 Oleyl Erucate 6 66 6 6 6 6 6 6 Decyl Oleate 6 6 6 6 6 6 6 6 6 Dimethicone 5 5 5 5 5 5 5 55 Tromethamine 1 1 1 1 1 1 1 1 1 Glycerin 5 5 5 5 5 5 5 5 5 Allantoin0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Water ad 100 4-29 4-30 4-31 4-324-33 4-34 4-35 4-36 Titanium dioxide 2 5 Benzylidene malonatepolysiloxane 1 2 1 Methylene Bis-Benztriazolyl 1 2 1Tetramethylbutylphenol Zinc oxide 5 2 UV-Pearl OMC 10 5 5 UV-Pearl,Ethylhexyl Dimethyl PABA 5 UV-Pearl, Homosalate 10 UV-Pearl, OCR, BP-315 UV-Pearl, Ethylhexyl Dimethyl PABA, 10 BP-3 UV-Pearl, Homosalate,BP-3 15 UV-Pearl, Ethylhexyl salicylate, BP-3 15 UV-Pearl OMC, BMDBM 15UV-Pearl, Ethylhexyl Dimethyl PABA, 15 BMDBM Polyglyceryl-3-Dimerate 3 33 3 3 3 3 3 Cera Alba 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 HydrogenatedCastor Oil 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Paraffinium Liquidum 7 7 7 77 7 7 7 Caprylic/Capric Triglyceride 7 7 7 7 7 7 7 7 Hexyl Laurate 4 4 44 4 4 4 4 PVP/Eicosene Copolymer 2 2 2 2 2 2 2 2 Propylene Glycol 4 4 44 4 4 4 4 Magnesium Sulfate 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Tocopherol0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tocopheryl Acetate 0.5 0.5 0.5 0.5 0.50.5 0.5 0.5 Cyclomethicone 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methylparabene0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Water ad 100 4-38 4-39 4-40 4-414-42 4-43 4-44 4-45 4-46 4-47 4-48 Titanium dioxide 2 5 3 3 Benzylidenemalonate polysiloxane 1 1 1 Methylene Bis-Benztriazolyl 1 2 1 1Tetramethylbutylphenol Zinc oxide 5 2 UV-Pearl OMC 5 5 5 5 7 5 5 5 5 5 8UV-Pearl, OCR 10 5 UV-Pearl, Ethylhexyl Dimethyl 10 PABA UV-Pearl,Homosalate 10 UV-Pearl, Ethylhexyl salicylate 10 UV-Pearl, OMC, BP-3 10UV-Pearl, OCR, BP-3 10 UV-Pearl, Ethylhexyl Dimethyl 10 PABA, BP-3UV-Pearl, Homosalate, BP-3 10 UV-Pearl, Ethylhexyl salicylate, BP-3 10BMDBM 2 UV-Pearl OMC, 4- 25 Methylbenzylidene CamphorPolyglyceryl-3-Dimerate 3 3 3 3 3 3 3 3 3 3 3 Cera Alba 0.3 0.3 0.3 0.30.3 0.3 0.3 0.3 0.3 0.3 0.3 Hydrogenated Castor Oil 0.2 0.2 0.2 0.2 0.20.2 0.2 0.2 0.2 0.2 0.2 Paraffinium Liquidum 7 7 7 7 7 7 7 7 7 7 7Caprylic/Capric Triglyceride 7 7 7 7 7 7 7 7 7 7 7 Hexyl Laurate 4 4 4 44 4 4 4 4 4 4 PVP/Eicosene Copolymer 2 2 2 2 2 2 2 2 2 2 2 PropyleneGlycol 4 4 4 4 4 4 4 4 4 4 4 Magnesium Sulfate 0.6 0.6 0.6 0.6 0.6 0.60.6 0.6 0.6 0.6 0.6 Tocopherol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.50.5 Tocopheryl Acetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5Cyclomethicone 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05Methylparabene 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15Water ad 100 4-49 4-50 4-51 4-52 4-53 4-54 4-55 Titanium dioxide 2 5 2 5Benzylidene malonate polysiloxane 0.5 Methylene Bis-Benztriazolyl 1Tetramethylbutylphenol Zinc oxide 2 UV-Pearl, OMC 14 5 5 UV-Pearl, OCR13 5 5 UV-Pearl, Ethylhexyl salicylate, BP-3 15 BMDBM 3 2 UV-Pearl, OMC,BMDBM 15 UV-Pearl, OCR, BMDBM 15 15 30 UV-Pearl, OMC,4-Methylbenzylidene 5 Camphor 4-Methylbenzyliden Camphor, 3Polyglyceryl-3-Dimerate 3 3 3 Cera Alba 0.3 0.3 0.3 2 2 2 2 HydrogenatedCastor Oil 0.2 0.2 0.2 Paraffinium Liquidum 7 7 7 Caprylic/CapricTriglyceride 7 7 7 Hexyl Laurate 4 4 4 PVP/Eicosene Copolymer 2 2 2Propylene Glycol 4 4 4 Magnesium Sulfate 0.6 0.6 0.6 Tocopherol 0.5 0.50.5 Tocopheryl Acetate 0.5 0.5 0.5 1 1 1 1 Cyclomethicone 0.5 0.5 0.5Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methylparabene 0.150.15 0.15 0.15 0.15 0.15 0.15 Dicocoyl Pentyerythrityl Citrate, Sorbitan6 6 6 6 Sesquioleate, Cera Alba, Aluminium Stearate PEG-7 HydrogenatedCastor Oil 1 1 1 1 Zinc Stearate 2 2 2 2 Oleyl Erucate 6 6 6 6 DecylOleate 6 6 6 6 Dimethicone 5 5 5 5 Tromethamine 1 1 1 1 Glycerin 5 5 5 5Allantoin 0.2 0.2 0.2 0.2 Water ad 100

TABLE 5 Oil-in-water sunscreen emulsions, values in % (weight/weight)5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 5-10 Titanium dioxide 2 5 3Benzylidene malonate polysiloxane 1 2 1 1 Methylene Bis-Benztriazolyl 12 1 Tetramethylbutylphenol Zinc oxide 5 2 UV-Pearl, OMC 30 15 15 15 1515 15 15 15 15 4-Methylbenzyliden Camphor BMDBM PhenylbenzimidazoleSulfonic Acid 4 Stearyl Alcohol (and) Steareth-7 3 3 3 3 3 3 3 3 3 3(and) Steareth-10 Glyceryl Stearate (and) Ceteth-20 3 3 3 3 3 3 3 3 3 3Glyceryl Stearate 3 3 3 3 3 3 3 3 3 3 Microwax 1 1 1 1 1 1 1 1 1 1Cetearyl Octanoate 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5Caprylic/Capric Triglyceride 6 6 6 6 6 6 6 6 6 6 Oleyl Oleate 6 6 6 6 66 6 6 6 6 Propylene Glycol 4 4 4 4 4 4 4 4 4 4 Glyceryl Stearate SEStearic Acid Persea Gratissima Propylparabene 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 0.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 0.15 0.15 Tromethamine 1.8 Glycerin Water ad ad ad ad ad ad adad ad ad 100 100 100 100 100 100 100 100 100 100 5-11 5-12 5-13 5-145-15 5-16 5-17 5-18 Titanium dioxide 3 2 2 5 Benzylidene malonatepolysiloxane 1 0.5 Methylene Bis-Benztriazolyl 1 1 0.5Tetramethylbutylphenol Zinc oxide 2 UV-Pearl, OMC 15 15 15 30 30 30 1515 4-Methylbenzyliden Camphor 3 BMDBM 1 Phenylbenzimidazole SulfonicAcid 4 Stearyl Alcohol (and) Steareth-7 3 3 3 3 (and) Steareth-10Glyceryl Stearate (and) Ceteth-20 3 3 3 3 Glyceryl Stearate 3 3 3 3Microwax 1 1 1 1 Cetearyl Octanoate 11.5 11.5 11.5 11.5 Caprylic/CapricTriglyceride 6 6 6 6 14 14 14 14 Oleyl Oleate 6 6 6 6 Propylene Glycol 44 4 4 Glyceryl Stearate SE 6 6 6 6 Stearic Acid 2 2 2 2 PerseaGratissima 8 8 8 8 Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.050.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Tromethamine1.8 Glycerin 3 3 3 3 Water ad ad ad ad ad ad ad ad 100 100 100 100 100100 100 100 5-19 5-20 5-21 5-22 5-23 5-24 5-25 5-26 5-27 5-28 Titaniumdioxide 3 3 2 Benzylidene malonate polysiloxane 1 2 1 1 1 0.5 MethyleneBis-Benztriazolyl 1 2 1 1 1 0.5 Tetramethylbutylphenol Zinc oxide 5 2 2UV-Pearl, OMC 15 15 15 15 15 15 15 15 15 15 Caprylic/Capric Triglyceride14 14 14 14 14 14 14 14 14 14 Oleyl Oleate Propylene Glycol GlycerylStearate SE 6 6 6 6 6 6 6 6 6 6 Stearic Acid 2 2 2 2 2 2 2 2 2 2 PerseaGratissima 8 8 8 8 8 8 8 8 8 8 Propylparabene 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 0.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 0.15 0.15 Glyceryl Stearate, Ceteareth-20, Ceteareth-10,Cetearyl Alcohol, Cetyl Palmitate Ceteareth-30 Dicaprylyl EtherHexyldecanol, Hexyldexyllaurate Cocoglycerides Tromethamine Glycerin 3 33 3 3 3 3 3 3 3 Water ad ad ad ad ad ad ad ad ad ad 100 100 100 100 100100 100 100 100 100 5-29 5-30 5-31 5-32 5-33 5-34 5-35 5-36 Titaniumdioxide 2 5 Benzylidene malonate polysiloxane 1 MethyleneBis-Benztriazolyl 1 Tetramethylbutylphenol UV-Pearl, OMC 15 7.5 7.5 2030 10 10 UV-Pearl, OCR 10 10 UV-Pearl, Ethylhexyl salicylate, BP-3 5UV-Pearl, OMC, BMDBM 20 UV-Pearl, OCR, BMDBM 5 4-MethylbenzylidenCamphor 3 BMDBM 1 Phenylbenzimidazole Sulfonic Acid 4 4 Stearyl Alcohol(and) Steareth-7 (and) 3 Steareth-10 Glyceryl Stearate (and) Ceteth-20 3Glyceryl Stearate 3 Microwax 1 Cetearyl Octanoate 11.5 Caprylic/CapricTriglyceride 6 14 14 14 14 Oleyl Oleate 6 Propylene Glycol 4 GlycerylStearate SE 6 6 6 6 Stearic Acid 2 2 2 2 Persea Gratissima 8 8 8 8Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methylparabene0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Glyceryl Stearate, Ceteareth-20,Ceteareth- 8.6 8.6 8.6 10, Cetearyl Alcohol, Cetyl PalmitateCeteareth-30 3.9 3.9 3.9 Dicaprylyl Ether 7 7 7 Hexyldecanol,Hexyldexyllaurate 3 3 3 Cocoglycerides 3 3 3 Tromethamine 1.8 1.8Glycerin 3 3 3 3 Water ad 100

TABLE 6 Sunscreen Gels, values in % (weight/weight) 6-1 6-2 6-3 6-4 6-56-6 6-7 6-8 6-9 6-10 a = aqueaous gel Titanium dioxide 2 5 3 Benzylidenemalonate polysiloxane 1 1 2 1 1 Methylene Bis-Benztriazolyl 1 1 2 1Tetramethylbutylphenol Zinc oxide 2 5 2 UV-Pearl, Ethylhexyl 30 15 15 1515 15 15 15 15 15 Mehtoxycinnamat 4-Methylbenzyliden Camphor 2 BMDBM 1Phenylbenzimidazole Sulfonic Acid 4 Prunus Dulcis 5 5 5 5 5 5 5 5 5 5Tocopheryl Acetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5Caprylic/Capric Triglyceride 3 3 3 3 3 3 3 3 3 3 Octyldodecanol 2 2 2 22 2 2 2 2 2 Decyl Oleate 2 2 2 2 2 2 2 2 2 2 PEG-8 (and) Tocopherol(and) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 AscorbylPalmitate (and) Ascorbic Acid (and) Citric Acid Sorbitol 4 4 4 4 4 4 4 44 4 Polyacrylamide (and) C13–14 3 3 3 3 3 3 3 3 3 3 Isoparaffin (and)Laureth-7 Carbomer Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 Allantoin Tromethamine 1.8 Water ad ad ad ad ad ad ad ad ad ad100 100 100 100 100 100 100 100 100 100 6-11 6-12 6-13 6-14 6-15 6-166-17 6-18 a = aqueaous gel a a a a a Titanium dioxide 3 2 Benzylidenemalonate polysiloxane 1 0.5 1 2 Methylene Bis-Benztriazolyl 1 1 0.5 1 21 Tetramethylbutylphenol Zinc oxide 2 UV-Pearl Ethylhexyl 15 15 15 15 1515 15 15 Mehtoxycinnamat 4-Methylbenzyliden Camphor BMDBMPhenylbenzimidazole Sulfonic Acid Prunus Dulcis 5 5 5 Tocopheryl Acetate0.5 0.5 0.5 Caprylic/Capric Triglyceride 3 3 3 Octyldodecanol 2 2 2Decyl Oleate 2 2 2 PEG-8 (and) Tocopherol (and) 0.05 0.05 0.05 AscorbylPalmitate (and) Ascorbic Acid (and) Citric Acid Sorbitol 4 4 4 5 5 5 5 5Polyacrylamide (and) C13–14 3 3 3 Isoparaffin (and) Laureth-7 Carbomer1.5 1.5 1.5 1.5 1.5 Propylparabene 0.05 0.05 0.05 Methylparabene 0.150.15 0.15 0.15 0.15 0.15 0.15 0.15 Allantoin 0.2 0.2 0.2 0.2 0.2Tromethamine 2.4 2.4 2.4 2.4 2.4 Water ad ad ad ad ad ad ad ad 100 100100 100 100 100 100 100 6-19 6-20 6-21 6-22 6-23 6-24 6-25 6-26 6-276-28 w = wassrig a a a a a a a a a a Titanium dioxide MethyleneBis-Benztriazolyl 1 2 1 Tetramethylbutylphenol Zinc oxide UV-Pearl, OMC30 30 15 15 15 11 12 15 15 15 UV-Pearl, OCR UV-Pearl, OMC, MethyleneBis- Benztriazolyl Tetramethylbutylphenol UV-Pearl, Ethylhexylsalicylate, BMDBM Disodium Phenyl Dibenzimidazole TetrasulfonatePhenylbenzimidazole Sulfonic Acid 4 4 Prunus Dulcis Tocopheryl AcetateCaprylic/Capric Triglyceride Octyldodecanol Decyl Oleate PEG-8 (and)Tocopherol (and) Ascorbyl Palmitate (and) Ascorbic Acid (and) CitricAcid Sorbitol 5 5 5 5 5 5 5 5 5 5 Polyacrylamide (and) C13–14Isoparaffin (and) Laureth-7 Carbomer 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.51.5 Propylparabene Methylparabene 0.15 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 0.15 Allantoin 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2Tromethamine 2.4 4.2 4.2 2.4 2.4 2.4 2.4 2.4 2.4 2.4 Water ad ad ad adad ad ad ad ad ad 100 100 100 100 100 100 100 100 100 100 6-29 6-30 6-316-32 6-33 6-34 6-35 6-36 w = wassrig a a a a a Titanium dioxide 3 2 5Methylene Bis-Benztriazolyl 1 1 0.5 1 2 1 Tetramethylbutylphenol Zincoxide 2 UV-Pearl, OMC 15 10 10 10 10 15 10 UV-Pearl, OCR 10 UV-Pearl,OMC, Methylene Bis- 7 6 Benztriazolyl Tetramethylbutylphenol UV-Pearl,Ethylhexyl salicylate, 10 BMDBM Disodium Phenyl Dibenzimidazole 3 3 3Tetrasulfonate Phenylbenzimidazole Sulfonic Acid 2 2 3 3 Prunus Dulcis 55 5 Tocopheryl Acetate 0.5 0.5 0.5 Caprylic/Capric Triglyceride 3 3 3Octyldodecanol 2 2 2 Decyl Oleate 2 2 2 PEG-8 (and) Tocopherol (and)0.05 0.05 0.05 Ascorbyl Palmitate (and) Ascorbic Acid (and) Citric AcidSorbitol 4 4 4 5 5 5 5 5 Polyacrylamide (and) C13–14 3 3 3 Isoparaffin(and) Laureth-7 Carbomer 1.5 1.5 1.5 1.5 1.5 Propylparabene 0.05 0.050.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Allantoin0.2 0.2 0.2 0.2 0.2 Tromethamine 2.4 2.4 2.4 2.4 2.4 Water ad ad ad adad ad ad ad 100 100 100 100 100 100 100 100 6-37 6-38 6-39 6-40 6-416-42 6-43 6-44 6-45 6-46 Titanium dioxide 2 5 3 Benzylidene malonatepolysiloxane 1 1 2 1 1 Methylene Bis-Benztriazolyl 1 1 2 1Tetramethylbutylphenol Zinc oxide 2 5 2 UV-Pearl, OMC 30 5 5 5 5 5 5 5 55 UV-Pearl, OCR 10 UV-Pearl, Ethylhexyl Dimethyl 10 PABA UV-Pearl,Homosalate 10 UV-Pearl, Ethylhexyl salicylate 10 UV-Pearl, OMC, BP-3 10UV-Pearl, OCR, BP-3 10 UV-Pearl, Ethylhexyl Dimethyl 10 PABA, BP-3UV-Pearl, Homosalate, BP-3 10 UV-Pearl, Ethylhexyl salicylate, BP-3 104-Methylbenzyliden Camphor 2 BMDBM 1 Phenylbenzimidazole Sulfonic Acid 4Prunus Dulcis 5 5 5 5 5 5 5 5 5 5 Tocopheryl Acetate 0.5 0.5 0.5 0.5 0.50.5 0.5 0.5 0.5 0.5 Caprylic/Capric Triglyceride 3 3 3 3 3 3 3 3 3 3Octyldodecanol 2 2 2 2 2 2 2 2 2 2 Decyl Oleate 2 2 2 2 2 2 2 2 2 2PEG-8, Tocopherol, Ascorbyl Palmitate, 0.05 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 Ascorbic Acid, Citric Acid Sorbitol 4 4 4 4 4 4 4 44 4 Polyacrylamide (and) C13–14 3 3 3 3 3 3 3 3 3 3 Isoparaffin (and)Laureth-7 Propylparabene 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.050.05 Methylparabene 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15Tromethamine 1.8 Water ad 100 6-47 6-48 6-49 6-50 6-51 6-52 6-53 6-54 a= aqueaous gel a a a a a Titanium dioxide 3 2 Benzylidene malonatepolysiloxane 1 0.5 1 2 Methylene Bis-Benztriazolyl 1 1 0.5 1 2 1Tetramethylbutylphenol Zinc oxide 2 UV-Pearl, OMC 5 5 5 5 5 5 5 5UV-Pearl, OCR, BP-3 5 UV-Pearl, OMC, BMDBM 10 UV-Pearl, OCR, BMDBM 10UV-Pearl, Homosalate, BMDBM 10 UV-Pearl, Ethylhexyl salicylate, BMDBM 10UV-Pearl, OMC, 4-Methylbenzylidene 10 Camphor UV-Pearl, OCR,4-Methylbenzylidene 10 Camphor UV-Pearl, Ethylhexyl Dimethyl PABA, 4- 10Methylbenzylidene Camphor UV-Pearl, Ethylhexyl salicylate, 4- 5Methylbenzylidene Camphor Prunus Dulcis 5 5 5 Tocopheryl Acetate 0.5 0.50.5 Caprylic/Capric Triglyceride 3 3 3 Octyldodecanol 2 2 2 Decyl Oleate2 2 2 PEG-8; Tocopherol; Ascorbyl Palmitate; 0.05 0.05 0.05 AscorbicAcid; Citric Acid Sorbitol 4 4 4 5 5 5 5 5 Polyacrylamide,C_(13–14)Isoparaffin, 3 3 3 Laureth-7 Carbomer 1.5 1.5 1.5 1.5 1.5Propylparabene 0.05 0.05 0.05 Methylparabene 0.15 0.15 0.15 0.15 0.150.15 0.15 0.15 Allantoin 0.2 0.2 0.2 0.2 0.2 Tromethamine 2.4 2.4 2.42.4 2.4 Water ad 100

LIST OF FIGURES

FIG. 1: Photo-acoustic response. Given as signal in a.u. (arbitraryunits) versus time coming from the skin during the in vivo application.Non-encapsulated OMC versus Eusolex® UV-Pearls™ OMC. The upper partrepresents the monitoring for OMC at a wavelength of 266 nm. Underneath,the behavior of the formulation itself is monitored at 355 nm as acontrol experiment.

FIG. 2: Distribution profile of Eusolex® UV-Pearls™ OMC in the hornylayer of porcine skin after in vitro application. The distance betweentwo horizontal lines represents the amount of stratum corneum (SC) perstrip. The SC amount varies from strip to strip but on average itdecreases with increasing strip number. The horizontal length of thecolumn represents the concentration of the OMC. 100% of stratum corneumcorrespond to 20 μm.

FIG. 3: Distribution profile of free OMC in the horny layer of porcineskin after in vitro application. The distance between two horizontallines represents the amount of stratum corneum (SC) per strip. The SCamount varies from strip to strip but on average it decreases withincreasing strip number. The horizontal length of the column representsthe concentration of the OMC. 100% of stratum corneum correspond to 20μm.

FIG. 4: Comparison of the cumulative release of OMC as a function oftime (hrs) during the first 6 hours from each of the twoformulations—OMC free formulated (solid line, ▬), and Eusolex®UV-Pearls™ OMC (dotted line, - - ) through. Tuffryn® following finitedosing (5 mg/cm²), mean±SD, n=3.

FIG. 5: Epidermal uptake of OMC by epidermal membranes (heat-separatedfrom the dermis) after 6 hours of exposure to each formulation followingfinite dosing (5 mg/cm²).

1. A composition having UV protection properties comprising A) at leastone encapsulated organic sunscreen, and B) at least one micronizedorganic UV filter, wherein the skin penetration capability of thecomposition is reduced by at least 10% compared to compositions with thesame, but unencapsulated, organic sunscreen.
 2. A composition accordingto claim 1, wherein the skin penetration is reduced by at least 20%compared to compositions with the same, but unencapsulated, organicsunscreen.
 3. A composition according to claim 1, wherein the at leastone encapsulated organic sunscreen is encapsulated in capsulespredominantly containing an organic polymeric material and/or inorganicoxidic material.
 4. A composition according to claim 1, wherein thecapsules have an average particle size in the range of about 10 nm toabout 10000 nm.
 5. A composition according to claim 1, wherein thecomposition comprises no organic sunscreen agents in soluble form.
 6. Acomposition according to claim 1, wherein the composition comprises atleast one inorganic sunscreen agent.
 7. A composition according to claim1, wherein at least one organic sunscreen is immobilized by beingcoupled to a surface or a polymeric chain.
 8. A composition according toclaim 1, which comprises at least one polymeric UV filter.
 9. Acomposition according to claim 1, wherein the at least one micronizedorganic UV filter is a triazine compound, benzotriazole compound, vinylgroup-containing amide compound, cinnamic acid amide compound orsulfonated benzimidazole compound.
 10. A composition according to claim1, which comprises 3-(4′-methylbenzylidene)-dl-camphor,1-(4-tert-butylphenyl)-3 -(4-methoxyphenyl)propane-1,3-dione,4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octylmethoxycinnamate, 3,3,5-trimethylcyclohexyl salicylate, 2-ethylhexyl4-(dimethylamino)benzoate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, ora potassium, sodium or triethanolamine salt thereof, or coated titaniumdioxide.
 11. A composition according to claim 1, which is a hydrogel.12. A composition according to claim 1, which is a cosmetic formulation.13. A composition according to claim 1, which is a pharmaceuticalformulation.
 14. A method for the prophylaxis of damage to the skincaused by sunrays comprising administering to the skin a compositionaccording to claim
 1. 15. A method according to claim 14, wherein thecomposition is a cosmetic composition.
 16. A method for preparing asunscreen composition according to claim 1, comprising mixing togetherat least one encapsulated organic sunscreen and at least one micronizedorganic UV filter.
 17. A composition according to claim 1, wherein thecapsules have an average particle size in the range of about 10 nm toabout 5000 nm.
 18. A composition according to claim 1, wherein thecomposition comprises zinc or titanium dioxide.
 19. A compositionaccording to claim 1, wherein at least one organic sunscreen isimmobilised by being coupled to a surface of an inorganic sunscreenparticle or a siloxane polymeric chain.
 20. A method for the prophylaxisof sunburn or sun-caused erythrema of the skin comprising administeringto the skin a composition according to claim 1.